CN108396143B - A method of molybdenum is removed from tungstate solution extraction - Google Patents
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Abstract
The invention discloses a kind of methods for removing molybdenum from tungstate solution extraction.This method realizes the deep purifying of high-content molybdenum using two sections of vulcanizations-solvent-extracted mode.It is handled by first cure, makes most two thiomolybdates of molybdenum fast transition and three thiomolybdates in solution, then extract molybdenum most of in solution to organic phase by one-section abstraction；Remaining a small amount of molybdenum, is vulcanized by second segment depth in solution, make molybdenum be further transformed to the stronger tetrathio molybdate of extractant affinity, then by the way of vacuum volatilization, the vulcanizing agent of liquid surplus after vulcanization is removed and is recycled；Molybdenum, is removed in depth by two-stage extraction, is purified liquid by Vacuum Desulfurization treated solution.Vulcanizing agent utilization rate of the present invention is high, total dosage is low, and in organic phase stripping process, oxidant consumption amount is few, and oxidation heat liberation phenomenon is significantly alleviated, and is conducive to extend the service life of organic phase.Except molybdenum whole process generates the deeply removing molybdenum, it can be achieved that high molybdenum solution without waste residue.
Description
Technical field
The present invention relates to a kind of solution purification impurity-removing method, especially a kind of method for removing molybdenum from tungstate solution extraction.
Background technique
Tungsten separation is always to perplex the technical problem of Tungsten smelting.Based on the nuance of the certain properties of tungsten, develop
Various forms of separation methods such as the precipitation method, resin adsorption method, solvent extraction.Wherein, the property of tungsten oxyphie, molybdenum parent's sulphur
Difference is more significant, and most tungstate solutions are unfolded according to this except the research of molybdenum, majority obtained industrial application except molybdenum method
It is based on the principle.As high-quality tungsten mineral resource gradually decreases, Tungsten smelting system molybdenum content is constantly increased, and is based on sulphur to existing
Change reaction except molybdenum technique causes biggish pressure, the consumption of vulcanizing agent and subsequent oxidation agent dramatically increases.At the same time,
The time of vulcanization reaction needs further to extend, and can realize the complete cure of molybdenum.
Since molybdenum content increases, to make molybdenum complete cure tetrathio molybdate, vulcanizing agent used in amounts is more than theoretical amount
2.5 times, i.e. sulphur molybdenum the mass ratio of the material is greater than 10 times.It is molten while molybdenum is with the extraction of tetrathio molybdate for solvent extraction
Superfluous negative divalent sulfur of dissociating can also be extracted to organic phase in liquid.Therefore, it is needed in stripping process with enough oxidants, it will
All negative divalent sulfur exhaustive oxidations, can realize the complete desorption of molybdenum in organic phase.Negative divalent sulfur content is higher in organic phase,
The heat release of oxidation reaction is more violent, and reaction temperature not only causes the significant volatilization of diluent kerosene up to 90 DEG C or more in this way,
The degradation for accelerating extractant, is unfavorable for industrial application.
Summary of the invention
The object of the present invention is to provide in a kind of lower situation of vulcanizing agent dosage that high-content molybdenum in tungstate solution is deep
The method for spending removing, can both reduce the consumption of vulcanizing agent and oxidant, can also shorten vulcanization time, alleviate putting for oxidation back extraction
Thermal phenomenon extends organic phase service life cycle.
Technical solution of the present invention: a method of molybdenum being removed from tungstate solution extraction, is included the following steps.
(1) tungstate solution containing molybdenum is subjected to one step cure processing, vulcanizing agent is added, sulphur molybdenum the mass ratio of the material is 2 ~ 3
Between, so that the molybdate in solution is converted into two thiomolybdates and three thiomolybdates, liquid after obtained one step cure.
Tungstic acid content is not more than 250g/L in the tungstate solution containing molybdenum, and molybdenum content is in 3 ~ 30g/L.Described
Vulcanizing agent is one or more of mixtures of vulcanized sodium, hydrogen sulfide, ammonium sulfide, NaHS.The one step cure processing
Reaction temperature is 10 ~ 70 DEG C, and the reaction time is 0.5 ~ 2 hour.
(2) two sections obtained liquid after one step cure that step (1) obtains and new organic phase or step (5) are except molybdenum organic phase
Mixing carries out one-section abstraction except molybdenum operates, and obtains one section except liquid after molybdenum and one section remove molybdenum organic phase.
The new organic phase is using adogen as extractant, to be greater than or equal to 8 monohydric alcohol containing carbon number
For phase modifier, using kerosene as diluent.Extraction agent content is 5 ~ 25 wt.%, and phase modifier content is 5 ~ 30 wt.%.It is described
One-section abstraction is 10 ~ 40 DEG C except the extraction temperature of molybdenum operation, and extraction time is 5 ~ 30 minutes.It is most in liquid after one step cure
Two thiomolybdates and three thiomolybdates are extracted into organic phase, obtain lower one section of molybdenum content except liquid after molybdenum.
(3) liquid carries out post vulcanization processing after one section for obtaining step (2) removes molybdenum, and vulcanizing agent is added, sulphur molybdenum substance
Ratio is measured between 6 ~ 12, so that the molybdenum in solution is completely transformed into tetrathio molybdate, liquid after obtained post vulcanization.
The vulcanizing agent is one or more of mixtures of vulcanized sodium, hydrogen sulfide, ammonium sulfide, NaHS.It is described
The reaction temperature of post vulcanization processing is 10 ~ 70 DEG C, and the reaction time is 2 ~ 8 hours.
(4) liquid carries out Vacuum Desulfurization processing after the post vulcanization for obtaining step (3), makes to have neither part nor lot in vulcanization reaction surplus
Vulcanizing agent volatilization, obtains containing liquid after the less Vacuum Desulfurization of negative divalent sulfur that dissociates.The vulcanizing agent evaporated is used and was not added
The tungstate solution of the high molybdenum of vulcanizing agent is contacted and is absorbed.
The vacuum degree of the Vacuum Desulfurization is -20 ~ -95 kPa, and temperature is 40 ~ 90 DEG C, and the reaction time is 0.5 ~ 2 small
When.
(5) the regeneration organic phase for obtaining liquid after Vacuum Desulfurization that step (4) obtains and new organic phase or step (6) is mixed
It closes, carries out two-stage extraction except molybdenum operates, be purified liquid and two sections are removed molybdenum organic phase.
The new organic phase is using adogen as extractant, to be greater than or equal to 8 monohydric alcohol containing carbon number
For phase modifier, using kerosene as diluent.Extraction agent content is 5 ~ 25 wt.%, and phase modifier content is 5 ~ 30 wt.%.It is described
Two-stage extraction is 10 ~ 40 DEG C except the extraction temperature of molybdenum operation, and extraction time is 5 ~ 30 minutes.It is most in liquid after post vulcanization
Tetrathio molybdate be extracted to organic phase, realize molybdenum depth removal, be purified liquid.
(6) one section for obtaining step (2) is mixed except molybdenum organic phase with oxidant and stripping agent, carries out oxidation back extraction behaviour
Make, obtains rich molybdenum liquid and regeneration organic phase.
The oxidant is hydrogen peroxide or sodium hypochlorite.The stripping agent is ammonium chloride, ammonium hydroxide, sodium chloride, hydrogen-oxygen
Change one or more of mixtures of sodium.The Stripping times of the oxidation back extraction operation are 20 ~ 60 minutes, and back extraction temperature is lower than 60
℃.After oxidation back extraction, most of molybdenum is oxidized to molybdate and enters solution, obtains rich molybdenum liquid and regeneration organic phase.
The present invention realizes the deep purifying of high-content molybdenum using two sections of vulcanizations-solvent-extracted mode.Pass through first segment sulphur
Change processing makes in solution most molybdenums be changed into the thiomolybdate of incomplete thioated in the lower situation of vulcanizing agent dosage,
Predominantly two thiomolybdates and three thiomolybdates, then extracted molybdenum most of in solution to organic phase by one-section abstraction；It is molten
Remaining a small amount of molybdenum, is vulcanized by second segment depth in liquid, in the excessive situation of vulcanizing agent dosage, molybdenum is made to be changed into and extract
The stronger tetrathio molybdate of agent affinity, then by the way of vacuum volatilization, simultaneously by the vulcanizing agent removing of liquid surplus after vulcanization
It recycles；Molybdenum, is removed in depth by two-stage extraction, is purified liquid by Vacuum Desulfurization treated solution.
The total dosage of vulcanizing agent of the present invention significantly reduces, and sulphur molybdenum the mass ratio of the material is lower than 4, and the molybdenum majority into organic phase is low
The thiomolybdate of thioated.In stripping process, because the negative divalent sulfur content of organic phase is low, oxidant consumption amount is accordingly reduced, oxygen
Change exothermic phenomenon to be relieved, is conducive to extend the service life of organic phase.Due to two thiomolybdates and three thiomolybdates
It is easier to generate compared with tetrathio molybdate, thus vulcanization time of the present invention and except the process cycle of molybdenum entirety is greatly shortened.
The invention has the advantages that the tungstate solution of processing 3 ~ 30g/L Han molybdenum, vulcanizing agent dosage is less, vulcanization time
Under conditions of shorter, through one step cure-solvent extraction except molybdenum operates, molybdenum content can be reduced to 0.5 ~ 2g/L or so；Molybdenum mainly with
The form of two thiomolybdates and three thiomolybdates enters organic phase, and strip stages oxidant consumption amount is accordingly reduced, oxidation
Exothermic phenomenon is relieved, and is conducive to extend organic phase service life；The negative divalent sulfur of post vulcanization surplus, can be waved by vacuum
The mode of hair removes in solution, and the vulcanization evaporated is absorbed with the tungstate solution for the high molybdenum that vulcanization reaction does not occur
Agent makes superfluous vulcanizing agent participate in the vulcanization reaction of molybdenum again to be recycled；It can be by molybdenum content in tungstate solution
It is reduced to 0.01g/L or so, realizes the deeply removing molybdenum of high molybdenum solution, except molybdenum whole process is generated without waste residue.
Detailed description of the invention
Fig. 1 is the process flow chart of the method for the present invention from tungstate solution extraction except molybdenum.
Specific embodiment
Embodiment 1
For sulphur is added by sulphur molybdenum the mass ratio of the material 3 containing the coarse sodium tungstate that tungstic acid is 249g/L, molybdenum is 3g/L
Change sodium solution, be slowly added to ammonium chloride under vigorous stirring and adjust pH value to 9.5, in 70 DEG C vulcanization reaction 0.5 hour, then with newly
It is organic to mix, it is extracted 15 minutes in 25 DEG C, obtains one-section abstraction organic phase and raffinate, molybdenum content is 0.52g/ in raffinate
L.By above-mentioned raffinate, sodium hydrosulfide is added by sulphur molybdenum the mass ratio of the material 6, in 70 DEG C vulcanization reaction 2 hours, then by solution
It is placed under conditions of 90 DEG C and vacuum degree -20kPa and volatilize desulfurization 0.5 hour, and contain tungstic acid be not added vulcanizing agent
The coarse sodium tungstate for being 3g/L for 249g/L, molybdenum absorbs the vulcanizing agent evaporated, and solution colour can be observed and turn yellow, and by
Gradually to orange transition, show that the vulcanizing agent evaporated takes part in the vulcanization reaction of molybdenum.By liquid after Vacuum Desulfurization and new organic phase
Mixing extracts 15 minutes in 25 DEG C, obtains two-stage extraction organic phase and molybdenum content as the scavenging solution of 0.008g/L.It is above-mentioned new organic
Mutually contain 25 wt.% adogens, 30 wt.% sec-octyl alcohols, 45 wt.% kerosene.Will containing 1mol/L sodium hydroxide,
0.5mol/L sodium hypochlorite, 1.5 mol/L sodium chloride mixed solution be slowly added under stirring to above-mentioned one-section abstraction
Organic phase, oxidation back extraction 20 minutes under conditions of temperature is lower than 60 DEG C, can be by sulfidion negative in organic phase and molybdenum dithiophosphate
Acid ion complete oxidation, and 96.8% molybdenum can be made to be stripped to water phase, obtain rich molybdenum liquid and regeneration organic phase.
A period Vacuum Desulfurization process is taken to absorb the coarse sodium tungstate containing molybdenum of vulcanizing agent, by the amount of sulphur molybdenum substance
Sodium sulfide solution is added than 2.5, is slowly added to ammonium chloride under vigorous stirring and adjusts pH value to 9.5, in 70 DEG C of vulcanization reactions 0.5
Hour, then with the two-stage extraction in a upper period except the organic of molybdenum mixes, extracted 5 minutes in 40 DEG C, it is organic to obtain one-section abstraction
Mutually and raffinate, molybdenum content is 0.59g/L in raffinate.By above-mentioned raffinate, sulphur hydrogenation is added by sulphur molybdenum the mass ratio of the material 10
Sodium solution, in 70 DEG C vulcanization reaction 2 hours, then solution is placed under conditions of 60 DEG C and vacuum degree -75kPa desulfurization 1.5 of volatilizing
Hour, and volatilized with absorbing containing the coarse sodium tungstate that tungstic acid is 249g/L, molybdenum is 3g/L for vulcanizing agent is not added
Solution colour flavescence can be observed in the vulcanizing agent come, and gradually to orange transition.Again by liquid after Vacuum Desulfurization and a upper period
Life is organic to be mixed, and is extracted 5 minutes in 40 DEG C, and the scavenging solution that molybdenum content is 0.006g/L is obtained.1mol/L hydroxide will be contained
Sodium, 1mol/L sodium hypochlorite, 1.5 mol/L sodium chloride mixed solution be slowly added under stirring to above-mentioned one-section abstraction
Organic phase, oxidation back extraction 40 minutes under conditions of temperature is lower than 60 DEG C, can be by sulfidion negative in organic phase and molybdenum dithiophosphate
Acid ion complete oxidation, and 98.5% molybdenum can be made to be stripped to water phase, obtain rich molybdenum liquid and regeneration organic phase.
Embodiment 2
For be 193g/L containing tungstic acid, the thick ammonium tungstate solution that molybdenum is 15.6g/L, by sulphur molybdenum the mass ratio of the material 2 plus
Enter ammonium sulfide solution, in 10 DEG C vulcanization reaction 2 hours, then with it is new it is organic mix, extracted 30 minutes in 10 DEG C, obtain a Duan Cui
Organic phase and raffinate are taken, molybdenum content is 1.52g/L in raffinate.By above-mentioned raffinate, sulphur is added by sulphur molybdenum the mass ratio of the material 9
Change ammonium salt solution, in 10 DEG C vulcanization reaction 8 hours, then solution is placed under conditions of 40 DEG C and vacuum degree -95kPa desulfurization 2 of volatilizing
Hour, and with vulcanizing agent is not added be 193g/L containing tungstic acid, the thick ammonium tungstate solution that molybdenum is 15.6g/L is absorbed and is volatilized
Solution colour flavescence can be observed in vulcanizing agent out, and gradually to orange transition, shows that the vulcanizing agent evaporated takes part in
The vulcanization reaction of molybdenum.Liquid after Vacuum Desulfurization is mixed with newly organic, is extracted 30 minutes in 10 DEG C, obtains two-stage extraction organic phase
The scavenging solution for being 0.012g/L with molybdenum content.Above-mentioned new organic phase adogen containing 15wt.%, 20 wt.% 16
Alcohol, 65 wt.% kerosene.By containing 2mol/L ammonium chloride, 2mol/L ammonium hydroxide, 1mol/L hydrogen peroxide mixed solution in stirring
Under be slowly added to above-mentioned one-section abstraction organic phase, oxidation back extraction 60 minutes under conditions of temperature is lower than 60 DEG C can will be organic
Negative sulfidion and thiomolybdate ion complete oxidation in phase, and 98.7% molybdenum can be made to be stripped to water phase, obtain rich molybdenum liquid
With regeneration organic phase.
A period Vacuum Desulfurization process is taken to absorb the thick ammonium tungstate solution containing molybdenum of vulcanizing agent, by the amount of sulphur molybdenum substance
Ammonium sulfide solutions are added than 2, in 45 DEG C vulcanization reaction 0.5 hour, then with the two-stage extraction in a upper period except the organic phase of molybdenum is mixed
It closes, is extracted 10 minutes in 25 DEG C, obtain one-section abstraction organic phase and raffinate, molybdenum content is 1.43g/L in raffinate.It will be above-mentioned
Raffinate, by sulphur molybdenum the mass ratio of the material 9 be added ammonium sulfide solution, in 45 DEG C vulcanization reaction 5 hours, then by solution be placed in 40 DEG C and
Volatilize desulfurization 2 hours under conditions of vacuum degree -95kPa, and be not added vulcanizing agent containing tungstic acid be 193g/L, molybdenum is
The thick ammonium tungstate solution of 15.6g/L absorbs the vulcanizing agent evaporated, solution colour flavescence can be observed, and gradually to orange mistake
It crosses.It mixed the regeneration in liquid after Vacuum Desulfurization and a upper period is organic, and was extracted 10 minutes in 25 DEG C, obtaining molybdenum content is
The scavenging solution of 0.011g/L.Mixed solution containing 2mol/L ammonium chloride, 2mol/L ammonium hydroxide, 1mol/L hydrogen peroxide is being stirred into shape
It is slowly added under state to above-mentioned one-section abstraction organic phase, oxidation back extraction 60 minutes, can will have under conditions of temperature is lower than 60 DEG C
Negative sulfidion and thiomolybdate ion complete oxidation in machine phase, and 98.3% molybdenum can be made to be stripped to water phase, obtain rich molybdenum
Liquid and regeneration organic phase.
Embodiment 3
For be 171g/L containing tungstic acid, the thick ammonium tungstate solution that molybdenum is 29.6g/L, by sulphur molybdenum the mass ratio of the material 3 plus
Enter ammonium sulfide solution, in 45 DEG C vulcanization reaction 2 hours, then with it is new it is organic mix, extracted 15 minutes in 40 DEG C, obtain a Duan Cui
Organic phase and raffinate are taken, molybdenum content is 2.18g/L in raffinate.Above-mentioned new organic phase adogen containing 5wt.%,
5 wt.% isooctanol, 90 wt.% kerosene.By above-mentioned raffinate, ammonium sulfide solution is added by sulphur molybdenum the mass ratio of the material 12, in 55 DEG C
Vulcanization reaction 4 hours, then liquid after above-mentioned post vulcanization is divided equally into four parts, a copy of it solution is handled without Vacuum Desulfurization,
Two-stage extraction is directly carried out except molybdenum operates；Other three parts of solution distinguishes Vacuum Desulfurization under conditions of 60 DEG C and vacuum degree -40kPa
1,2,3 hours, then mixed with new organic phase and carry out two-stage extraction except molybdenum operates.Two-stage extraction temperature is 40 DEG C, extraction time is
15 minutes, the molybdenum content in scavenging solution is measured after extraction respectively, the results are shown in Table 1.
The 1 Vacuum Desulfurization time of table removes the influence of molybdenum to two-stage extraction
| First part of solution | Second part of solution | Third part solution | 4th part of solution | |
| The Vacuum Desulfurization time (hour) | 0 | 1 | 2 | 3 |
| The molybdenum content (g/L) of scavenging solution | 0.156 | 0.047 | 0.025 | 0.016 |
Seen from table 1, vacuum volatilization is advantageous extraction except molybdenum process, this is because ammonium decompose the hydrogen that releases from
Son can promote the vulcanization reaction of molybdenum, promote the conversion ratio of tetrathio molybdate further.But the 4th part of solution Vacuum Desulfurization 3 is small
Shi Hou has a small amount of precipitating to generate, and therefore, the Vacuum Desulfurization time is unsuitable too long.
Claims (7)
1. a kind of method for removing molybdenum from tungstate solution extraction, which comprises the following steps:
(1) by containing molybdenum tungstate solution carry out one step cure processing, be added vulcanizing agent, sulphur molybdenum the mass ratio of the material between 2 ~ 3,
The molybdate in solution is set to be converted into two thiomolybdates and three thiomolybdates, liquid after obtained one step cure；
(2) two sections obtained liquid after one step cure that step (1) obtains and new organic phase or step (5) are except molybdenum organic phase is mixed
It closes, carries out one-section abstraction except molybdenum operates, obtain one section except liquid after molybdenum and one section remove molybdenum organic phase；
(3) liquid carries out post vulcanization processing after one section for obtaining step (2) removes molybdenum, and vulcanizing agent, sulphur molybdenum the mass ratio of the material is added
Between 6 ~ 12, the molybdenum in solution is made to be completely transformed into tetrathio molybdate, liquid after obtained post vulcanization；
(4) liquid carries out Vacuum Desulfurization processing after the post vulcanization for obtaining step (3), makes the vulcanization for having neither part nor lot in vulcanization reaction surplus
Agent volatilization obtains the vulcanizing agent evaporated containing liquid after the less Vacuum Desulfurization of negative divalent sulfur that dissociates use and vulcanization is not added
The tungstate solution of the high molybdenum of agent is contacted and is absorbed；
(5) it mixes regeneration that liquid after Vacuum Desulfurization that step (4) obtains and new organic phase or step (6) obtain is organic, into
Row two-stage extraction is operated except molybdenum, is purified liquid and two sections are removed molybdenum organic phase；
(6) one section for obtaining step (2) is mixed except molybdenum organic phase with oxidant and stripping agent, is carried out oxidation back extraction operation, is obtained
To rich molybdenum liquid and regeneration organic phase；
In step (1) and step (3), the vulcanizing agent is one kind or several of vulcanized sodium, hydrogen sulfide, ammonium sulfide, NaHS
The mixture of kind；In step (2) and (5), the new organic phase is using adogen as extractant, with big containing carbon number
In or equal to 8 monohydric alcohol be phase modifier, using kerosene as diluent, extraction agent content be 5 ~ 25 wt.%, phase modifier content
For 5 ~ 30 wt.%；In step (6), the oxidant is hydrogen peroxide or sodium hypochlorite；The stripping agent is ammonium chloride, ammonia
The mixtures of the one or more of water, sodium chloride, sodium hydroxide；The Stripping times of the oxidation back extraction operation are 20 ~ 60 minutes,
It is stripped temperature and is lower than 60 DEG C.
2. the method according to claim 1, wherein in step (1), three oxygen in the tungstate solution containing molybdenum
Change W content and be not more than 250g/L, molybdenum content is in 3 ~ 30g/L.
3. the method according to claim 1, wherein in step (1), the reaction temperature of the one step cure processing
It is 10 ~ 70 DEG C, the reaction time is 0.5 ~ 2 hour.
4. the method according to claim 1, wherein the one-section abstraction removes the extraction of molybdenum operation in step (2)
Temperature is 10 ~ 40 DEG C, and extraction time is 5 ~ 30 minutes.
5. the method according to claim 1, wherein in step (3), the reaction temperature of the post vulcanization processing
It is 10 ~ 70 DEG C, the reaction time is 2 ~ 8 hours.
6. the method according to claim 1, wherein in step (4), the vacuum degree of the Vacuum Desulfurization is-
20 ~ -95 kPa, temperature are 40 ~ 90 DEG C, and the reaction time is 0.5 ~ 2 hour.
7. the method according to claim 1, wherein the two-stage extraction removes the extraction of molybdenum operation in step (5)
Temperature is 10 ~ 40 DEG C, and extraction time is 5 ~ 30 minutes.
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